Ethylenically unsaturated sulfines and polymers thereof



United States Patent 3,269,991 ETHYLENICALLY UNSATURATED SULFINES ANDPOLYMERS THEREOF Edward M. La Combe, Charleston, W. Va., assignor tognifin Carbide Corporation, a corporation of New or i No Drawing. FiledNov. 29, 1963, Ser. No. 327,063

21 Claims. (Cl. 260--79.7)

This application is a continuation-in-part of copending applicationSerial No. 130,481, filed August 10, 1961, and issued March 1, 1966, asUnited States Patent No. 3,238,276, incorporated herein by reference.

The present invention is concerned with a novel and useful class ofpolymeric compositions, and is especially concerned with normally solidpolymers, including homopolymers and interpolymers, of certainalpha-ethylenically unsaturated sulfines, i.e. sulfonium compoundspossessing a terminal ethylenic unsaturation. The invention alsocontemplates the alpha-ethylenically unsaturated sulfine monomers hereindisclosed as novel compositions of matter.

More particularly, the alpha-ethylenically unsaturated sulfinescontemplated by this invention can be represented by the formula:

(I) R o 2 .aaawla] ma wherein R designates a hydrogen atom or a methylradical; R designates a saturated aliphatic hydrocarbon radicalcontaining from 1 to about 4, and preferably from 2 to 3 carbon atoms,such radical more preferably being unsubstituted in the positionadjacent to the oxygen atom to which it is directly connected; Rdesignates an alkyl radical containing from 1 to about 4, and preferablyfrom 1 to 2 carbon atoms; R designates a methyl or carboxymethyl (-CHCOOH) radical; X designates a halogen atom, such as a bromine, iodine orchlorine atom, or a methyl sulfate (OSO CH radical, and specificallydesignates a chlorine atom when R designates a carboxymethyl radical;and m designates an integer of from 1 to 2. Moreover, in those instanceswhen m is 1, the sulfonium radical Li] X is preferably attached to thatcarbon atom of the radical designated by R which is farthest from theadjacent oxygen atom, i.e. the carbon atom in the l-position. When m is2, the sulfonium radicals are preferably attached to vicinal carbonatoms of the radical designated by R and more preferably to thosevicinal carbon atoms of the radical which are farthest from the adjacentoxygen atom, i.e. the carbon atoms in the 1,2-position. In addition,when m is 2, R more preferably contains at least 3 carbon atoms.

As illustrative of such alpha-ethylenically unsaturated sulfines, therecan be mentioned acryloxymethyldimethylsulfonium methylsulfate,(2-acryloxyethyl) dimethylsulfonium methylsulfate,(2-acry1oxyethyl)dimethylsulfonium bromide,'(2-acryloxyethy1)dimethylsulfonium iodide,2-acryloxyethyl)methylethylsulfonium methylsulfate, 2-acryloxyethylmethylbutylsulfonium methylsulfate, 3 -acryloxypropyl dirnethylsulfoniummethylsulfate, (4-acryloxybutyl)dimethylsulfonium methylsulfate,(Z-methacryloxyethyl)dimethylsulfonium methylsulfate,(acryloxymethyl)carboxymethylmethylsulfonium chloride,

3,269,991 Patented August 30, 1966 this invention are the compoundsrepresented by the formulae:

wherein R, R R and X are as defin'ed above, and R designates a saturatedaliphatic hydrocarbon radical containing from 2 to 3 carbon atoms.

This invention is concerned, in one aspect, with normally solidhomopolymers of the aforementioned alphaethylenically unsaturatedsulfines.

The invention is also concerned with normally solid interpolymerscontaining, in polymerized form, on a theoretical monomer basis, atleast about 10 mole percent, and preferably at least about 50 molpercent of an alphaethylenically unsaturated sulfine, as defined above,together with an alpha-ethylenically unsaturated thio-ether representedby the formula:

wherein R, R R and m are as defined above. As illustrative of suchalpha-ethylenically unsaturated thio others, there can be mentioned:

methylthiomethyl acrylate Z-methylthioethyl acrylate, Z-ethylthioethylacrylate, 2-butylthioethyl acrylate, 3-methylthiopropyl acrylate,4-methylthiobutyl acrylate, Z-methylthioethyl methacrylate,2,3-bis(methylthio)propyl acrylate, 2,3-bis (methylthio) propylmethacrylate, 3,4-bis(methylthio)butyl acrylate,3,4-bis(methylthio)butyl methacrylate, etc.

The invention is concerned further with normally solid interpolymerscontaining, in polymerized form and on a theoretical monomer basis, atleast about 1 mole percent, preferably from about 5 to about molepercent, and more preferably from about 50 to about 95 mole percent ofan alphaethylenically unsaturated sulfine, as defined above, togetherwith an alpha-ethylenically unsaturated comonomer selected from thegroup consisting of (a) acrylonitrile and methacrylonitrile; (b) thevinyl alkanoates represented by the formula:

R 7OCH=GH: wherein R designates an alkyl radical preferably containingfrom 1 to about 7 carbon atoms and more preferably from 1 to 3 carbonatoms, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinylhexanoate, vinyl Z-ethylhexanoate, vinyl octanoate, etc., and (c) thealkyl and cyanoalkyl acrylates and methacrylates represented by theformula:

(VII) CHF-PJ-OR wherein R is defined above and R designates an alkyl orcyanoalkyl radical preferably containing from 1 to about 8 carbon atoms,and more preferably from 1 to 4 carbon atoms, such as methyl acrylate,methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-cyanoethylacrylate, 2-cyanoethyl methacrylate, butyl acrylate, 4- cyanobutylacrylate, hexyl acrylate, Z-ethylhexyl acrylate, octyl acrylate, octylmethacrylate, etc., and the like.

Thus, it is to be noted that the polymers of this invention, includeboth alpha-ethylenically unsaturated sulfine homopolymers, as well ascopolymers thereof with an alpha-ethylenically unsaturated thio-ether,or with an alpha-ethylenically unsaturated commoner as defined above. Inaddition, the polymers of this invention include terpolymers of analpha-ethylenically unsaturated sulfine with both an alpha-ethylenicallyunsaturated thio-ether and with an alpha-ethylenically unsaturatedcomonomer as defined above. Such terpolymers contain, in polymerizedform and on a theoretical monomer basis, (a) at least about 10 molepercent and preferably at least about 50 mole percent of thealpha-ethylenically unsaturated sulfine, when taken together with theamount of polymerized alpha-ethylenically unsaturated thio-etherpresent, and (b) at least about 1 mole percent, preferably from about 5to about 95 mole percent, and more preferably from about 50 to about 95mole percent of the alphaethylenically unsaturated sulfine, based uponthe total amount of polymerized monomers present. It is also to be notedthat the polymerized alpha-ethylenically unsaturated sulfine componentof the polymers of this invention can be composed of a mixture ofsulfines, such that more than one type of sulfonium radical is present.Similarly, more than one type of comonomer can also be present includingthose specifically described above, as well as a minor amount of othercopolymerizable monomers.

The polymers of this invention can be produced by several differenttechniques. For instance, the alphaethylenically unsaturated sulfine canbe obtained initially in monomeric form and subsequently polymerized byconventional processes for the polymerization of alphaethylenicallyunsaturated compounds either alone, so as to produce homopolymersthereof, or together with one or more comonomers, so as to producecopolymers or terpolymers thereof, etc. When desired initially inmonomeric form, the alpha-ethylenically unsaturated sulfine can readilybe obtained by reacting an alpha-ethylenically unsaturated thio-etherwith an alkylating agent in accordance with the equation:

wherein R, R R R X and m are as defined above. Reactions between athio-ether and an alkylating agent are in general discussed, forinstance, in Organic Chemistry, vol. 1, 2nd ed., by H. Gilman, JohnWiley & Sons, N.Y. 1948), page 867, such teachings being incorporatedherein by reference. Concordant therewith, by way of illustration, thealkylation can be carried out by bringing the thio-ether and thealkylating agent into reactive admix ture, in a suitable solvent ordiluent, if desired, at a temperature of from about 25 C. or slightlylower, up to about C. to C., or slightly higher. In addition, a smallamount of a conventional polymerization inhibitor, such as hydroquinone,or the like, is preferably incorporated in the reaction mixture. Astypical of the alkylating agents which can be employed in this regardthere can be mentioned dimethyl sulfate, methyl halides such as methylbromide, methyl chloride and methyl iodide, chloroacetic acid, etc.Moreover, the reaction is preferably carried out in a diluent which is asolvent for the thio-ether but a non-solvent for the resulting sulfineproduct, such as benzene, isopropyl ether, etc. Upon completion of thereaction, the sulfine product can be separated and recovered in anyconvenient manner.

The polymers of this invention can thereafter be obtained byconventional polymerization processes. Thus, for instance, solutionpolymerization techniques can be utilized wherein an inert organicsolvent solution of the alpha-ethylenically unsaturated sulfine alone,or in admixture with one or more comonomers in proportions ashereinabove described in connection with the polymer composition, iscontacted with a catalytic amount of a polymerization catalyst andmaintained at a temperature at which polymerization will occur for aperiod of time sufficient to produce a polymer product. A particularlyuseful solvent which can be utilized in this connection is.acetom'trile, although any other suitable inert organic solvent, suchas acetone, N,N-dimethylformamide, dimethylsulfone,N,N-dimethylacetamide, ethylene carbonate, ethylene carbamate,-gamma-butyrolactone, N-methy-l-Z-pyrrolidone, etc., can also beemployed. Alternatively, bulk, suspension or emulsion polymerizationtechniques can also be used under otherwise similar reaction conditions,i.e., proportions, temperature, time, etc. Similarly, other diluentssuch as water, benzene, toluene, xylene, hexane, heptane, etc., can alsobe used.

The catalysts most frequently employed in the polymerization reactions,and especially in connection with solution polymerization techniques,are the free-tradical-type polymerization catalysts, such as the azocompounds, of which azo-2,2'-diisobutyronitrile, dimethylazo-2,2'-diisobutyrate, azo-2,2 bis(2,4 dimethylvaleronitrile), azo-2,2-diisobutytramide, and the like, are typical. Other free-radical-typepolymerization catalysts which can be employed are the peroxides, suchas hydrogen peroxide, acetyl peroxide, benzoyl peroxide, peracetic acid,potassium persulfate, calcium percarbonate, etc. The catalyst isordinarily incorporated in the polymerization reaction mixture in aconcentration of from about 0.01 percent to about 5 percent or more byweight, and preferably from about 0.2 to about 2 percent by weight,based upon the total weight of monomer present, although any catalyticamount thereof can be utilized.

The polymerization is generally elfected by bringing the monomers intocontact with the catalyst at a temperature of from about 10 C., orslightly lower, to about C., or slightly higher, accompanied by heatingor cooling as needed to maintain the temperature at the desired level.The polymerization time will depend upon a variety of factors, such asthe nature of the monomer(s), catalyst and/or diluent employed, thereaction temperature, etc., and can vary over a wide range. Forinstance, a suitable reaction period lies in the range of from about 1to about 200 hours, but is not necessarily limited thereto. In addition,the polymerization can be carried out under atmospheric,superatmospheric or subatmospheric pressures, as desired.

Under completion of the polymerization reaction, the polymer product canbe recovered in any convenient manner, such as by coagulation,filtration, centrifugation, etc. The reaction product can also beemployed directly in many uses for the polymer product, obviating therecovery of the polymer per se.

In an alternative manner to the polymerization technique describedabove, the alkylation of the alpha-ethylenically unsaturated thio-etherand the polymerization of the monomer(s) can be carried out in oneoperation by incorporating the alkylating agent in a polymerizationreaction mixture containing, as the polymerizable monomer(s), thealpha-ethylenically unsaturated thio-ether alone, or in admixture withan alpha-ethylenically unsaturated comonomer as defined above. In such aprocedure, it is to be noted, the reactants should be employed in a moleratio of at least about 0.1 mole and preferably at least about 0.5 moleup to about 5 or more of the alkylating agent per thio-ether radical {SRof the alpha-ethylenically unsaturated thio-ether. Moreover, when acomonomer is present, the alpha-ethylenically unsaturated thio-ethershould be employed in an amount sufficient to provide upon alkylationand polymerization, on a theoretical monomer basis, at least about 1mole percent, preferably from about 5 to about 95 mole percent, and morepreferably from about 50 to about 95 mole percent of a polymerizedalpha-ethylenically unsaturated su1fine,.based upon the total amount ofpolymerized monomers present in the resulting polymer. Such amount isreadily determinable by one skilled in the art in light of thisdisclosure. The polymerization reaction and the recovery of theresulting polymer, when desired, is carried out as otherwise describedabove.

The polymers of this invention can also be prepared by reacting thealkylating agent with an initially formed polymer, i.e. either ahomopolymer of an alpha-ethylenically unsaturated thio-ether, or acopolymer thereof with an alpha-ethylenica-lly unsaturated comonomer asdefined above, the alkylation and initial polymerization, as Well as therecovery of the polymer product, also being car ried out as otherwisedescribed above.

The novel alpha-ethylenically unsaturated sulfines of this inventionfind utility in various applications. They can, for instance, be used aschemical intermediates, and, like other known sulfines, can be employedas assistants for textile processing and printing, and as foaming,emulsifying and wetting agents. They can, of course, also be employed toproduce the novel polymers of this invention.

I The polymers of this invention, in turn, also find utility in a widevariety of applications. They can, for example, be used to produce filmssuitable for use as packaging and coatings. In addition, the watersoluble polymers, generally those containing, in polymerized form and ona theoretical monomer basis, at least about 50 mole percent of thealpha-ethylenically unsaturated sulfine, can be employed as fiocculentsfor aqueous anionic suspensions, i.e. aqueous suspensions which arestabilized by a negative charge, such as sewage, white water, silica orclay suspensions, etc. In particular, it has been found thatfiber-forming polymer compositions evidencing enhanced dye aflinity canbe produed by blending conventional fiber-forming acrylonitrile polymerswith minor amounts, i.e. from about 1 perent to about 30 percent bytotal weight, and preferably from about 5 percent to about 20 percent bytotal weight, of the novel polymers of this invention.

The fiber-forming acrylonitnile polymers include normally solidhomopolymers of acrylonitnie, as well as copolymers and terpolymersthereof with other alpha-ethylenically unsaturated comonomers, suchcopolymers and terpolymers containing the polymerized acrylonitrilecomponent in a concentration of at least about 35 percent by weightbased upon the total weight of the polymer. Illustrative in thisconnection of other alpha-ethylenically unsaturated comonomers which canbe polymerized with acrylonitrile to produce convention-a1 fiber-formingpolymers there can be mentioned vinyl chloride, vinylidene chloride,styrene, vinyl acetate, alcrylamide, methyl acrylate, etc. Thecontemplated acrylonitrile polymers, it is to be noted, are those whichare useful in the production of fibers designated as acrylic andmodacrylic fibers in accordance with the Federal Trade Commission Rulesand Regulations under the Textile Identification Act, enacted September2, 1958, and can be obtained in Well known manner, such for example, asby the processes disclosed in US. Patents 2,420,565, 2,603,620 and2,868,756, or by any other convenient means known to the art.

The improved dyeable, fiber-forming compositions can be prepared byblending the normally solid polymers, i.e., both the fiber-formingacrylonitnile polymers and the polymers of this invention, inproportions as hereinabove described, in conventional mixing equipment,such as dough mixers, roll mixers, Banbury mixers, or the like, or byfiuxing the solid polymers. The most effective method of mixing,however, involves treatment in the solution state, where-in the polymersare initially dissolved together in a suitable inert organic solvent,such as those descnibed above in connection with polymerizationreactions. The solution of the blended polymer compositions can then bespun into fibers by the conventional wet or dry spinning techniquesknown to the art. It is to be noted that during the blending or spinningoperaitons, other additives such as delusterants, heat and lightstabilizers, etc., can also be added to the fiber-forming compositions,if desired.

After both stretching the fibers to orient the molecules and develop thedesired tensile properties, and shrinking the fibers to improve theirthermal properties, the modified fibers produced as described above canbe employed in the many applications in which synthetic fibers aregenerally employed. Moreover, the modified fibers are readily dyed byconventional dyeing techniques with a wide variety of dyestuffs toproduce highly colored fibers of desirable properties. Such fibers aredyed to deeper shades and absorb more dye from the dye bath than do thefibers prepared from the corresponding unmodified acrylonitrile polymersof which they are in part composed.

The present invention can be illustrated further by the followingspecific exarnples of its practice, but it is not intended to be limitedthereby. In the examples, the molecular weight of the normally solidpolymers (i.e. solid at room temperature under atmospheric pressure) wasdetermined by measuring their reduced viscosity, which, particularlyprior to alkylatio-n, may vary from about 0.1 to about 5, or evenhigher, and most frequently from about 1 to about 3, when measured at atemperature of 30 C. from a solution containing 0.2 gram of the polymerin milliliters of N,N-dimethylformamide.

The term reduced viscosity is well known in the art, and designates avalue obtained by dividing the specific viscosity of a solution of thepolymer by the concentration of the polymer in the solution, theconcentration being measured in grams of polymer per 100 milliliters ofsolvent. The specific viscosity is obtained by dividing the differencebetween the viscosity of the polymer solution and the viscosity of thepure solvent by the viscosity of the solvent. In particular, the reducedviscosities set forth in the examples were calculated from the equation:

wherein N is the difference between the flow-time of the polymersolution and the flow-time of the solvent, N is the flow-time of thesolvent, and C is the concentration of the polymer in solution expressedin grams per 100 milliliters of solution. The reduced viscosity of apolymer is regarded as a measure of the molecular weight of the 7polymer, i.e., the degree of polymerization, with higher valuesindicating higher molecular weights.

Two methods were employed in quantitatively measuring the dye absorptionvalues set forth in the example, viz.:

PROCEDURE A In this procedure, a 0.1 gram sample of the dyed fabric isscoured with isopropanol to remove absorbed dyestuff and dissolved in100 milliliters of N,N-dimethy1- forrnamide. The transmission of thissolution at 590 millimicrons is measured using a Bausch and LombSpectronic 20 spectrophotometer. The amount of dyestufi in thissolution, which is equal to the amount of dyestuff absorbed by the 0.1gram sample of fabric, [is read directly from the curve of transmissionversus concentration of the dyestufi in N,N-dimethylformamide. By simpleproportion, the amount of dyestuff absorbed by the total weight offabric is calculated. Then the percent dye absorbed is calculated by theequation:

Amount of dye absorbed t t ta 1 b Amount of dye availabie 100 percen ofO laval a le dye absorbed by the fabric. The percent increase in dyeabsorption due to the inclusion of the polymers of this invention iscalculated as follows:

Percent total dye absorbed by sample X 100 Percent total dye absorbed bycontrol PROCEDURE B In this procedure, a 0.2 gram sample of the dyed andscoured fabric is dissolved in 50 milliliters of N,N- dirnethylformamidecontaining 0.25 milliliter of acetic acid. The transmission of thissolution at 525 millimicrons is measured using a Beckman Model Bspectrophotometer. The amount of dyestuff absorbed by the 0.2 gramsample of fabric, is read directly from the curve of transmission versusconcentration of the dyestufi in N,N- dimethylformamide. By simpleproportion, the amount of dyestuff absorbed by the total weight offabric is calculated. Then the percent dye absorbed by the fabric andthe percent increase in dye absorption due to the inclusion of thepolymers of this invention is calculated as described above in ProcedureA.

Example I To a 300 milliliter Pyrex pressure bottle there were charged73 grams of Z-methylthioethyl acrylate, 47 grams of chloroacetic acid,50 grams of acetonitrile and 0.06 gram of hydroquinone. The bottle waspurged with nitrogen, capped and tumbled in a constant temperaturerotary water bath maintained at a temperature of 75 C., wherein thebottle was allowed to remain over a weekend. The contents of the bottlewere then poured into 1200 milliliters of isopropyl ether with continuedstirring. In this manner, approximately 43 grams of (2-acryloxyethyl)carboxymethylmethylsulfonium chloride settled out, and was recovered asa liquid. Upon polymerization of the product by conventionalfree-radical polymerization techniques as described above, solidpoly[(2-acryloxyethyl) carboxymethylmethylsulfonium chloride] isobtained.

In like manner,3-methacryloxypropyl-1,2-bis(carboxymethylmethylsulfonium)dichloride isobtained by the reaction of 2,3-bis(methylthio)propyl methacrylate withchloroacetic acid, and from which poly[3-methacryloxypropyl 1,2bis(carboxymethylmethylsulfonium)dichloride] is produced by conventionalfree radical polymerization techniques as described above.

Example 11 To a 300 milliliter Pyrex pressure bottle, there were charged73 grams of Z-methylthioethyl acrylate, 63 grams of dimethyl sulfate,100 grams of benzene and 0.05 gram of hydroquinone. The bottle waspurged with nitrogen, capped and tumbled in a constant temperaturerotary water bath, maintained at a temperature of 50 C. for a period ofabout 23 hours. In this manner, (2-acryloxyethyl)dimethylsulfoniummethylsulfate settled out, and was recovered as a liquid in anessentially quantitative yield. Upon polymerization of the product byconventional free-radical polymerization techniques as described above,solid poly[2 acryloxyethyl)dimethylsulfonium methylsulfate] is obtained.

In similar manner, (2- methacryloxyethyl) dimethylsulfoniummethylsulfate was recovered as a liquid in an essentially quantitativeyield by the reaction of grams of 2-methylthioethyl methacrylate with 63grams of dimethyl sulfate as otherwise described above in this example.Upon polymerization of the product by conventional free-radicalpolymerization techniques as described above, solid poly[(2methacryloxycthyl)dimethylsulfonium methylsulfate] is obtained.

In like manner, 3-acryloxypropyl-1,2-bis(dimethylsulfonium)di(methylsulfate) is obtained by the reaction of2,3-bis(methylthio)propyl acrylate with dimethyl sulfate, and from whichpoly[3-acryloxypropyl-1,2-bis(dimethylsulfonium) di(methylsulfate)] isproduced by conventional free-radical polymerization techniques asdescribed above.

Example III To a 300 millilter Pyrex pressure bottle, there were charged18 grams of a methyl acrylate/Z-methylthioethyl methacrylate copolymer,6 grams of dimethylsulfate and 100 grams of acetonitrile. The copolymeremployed was comprised of approximately 76 percent by weight ofpolymerized methyl acrylate and 24 percent by weight of polymerized2-methylthioethyl methacrylate, and had a reduced viscosity of 1.57. Theamount of dimethyl sulfate employed was sufiicient to convertessentially all of the polymerized Z-methylthioethyl methacrylate to thecorresponding polymerized form of (Z-methacryloxyethyl)dimethylsulfoniummethylsulfate. The bottle was purged with nitrogen, capped and tumbledin a constant temperature rotary water bath, maintained at a temperatureof 50 C. for a period of 20 hours. The resulting polymer solution washazy, and was cleared by the addition of 50 milliliters of methanol. Thepolymer product was then coagulated in 1500 milliliters of isopropylether and thereafter decanted and washed in an additional 1000milliliters of isopropyl ether. Finally, the polymer product was driedat a temperature of 50 C. in an air circulating oven for a period of 90hours. In this manner, there were obtained 22.3 grams of a copolymercomprised of approximately 61 percent by weight of polymerized methylacrylate and 39 percent by weight of polymerized (Z-methacryloxyethyl)dimethylsulfonium methyl sulfate, i.e. approximately mole percent ofmethyl acrylate and 15 mole percent of(Z-methacryloxyethyl)dimethylsulfonium methylsulfate in polymerizedform, on a theoretical monomer basis. The copolymer product was found tocontain 8.7 percent by weight of sulfur. Infra-red analysis confirmedthe presence of the sulfate ion.

The copolymer product of this example was subsequently employed toimprove the dye affinity of fibers produced from a conventional,fiber-forming acrylonitrile polymer in the following manner. Twentygrams of the copolymer were dissolved in 1145 grams of acetonitrile. Tothis solution there were then added 380 grams of a fiber-formingterpolymer comprised of approximately 70 percent by weight ofpolymerized acrylonitrile, 20 percent by weight of polymerized vinylchloride, and 10 percent by weight of vinylidene chloride, (prepared asdescribed in US. 2,868,756), and 16 grams of a 50/50 by weight mixtureof dioctyltin maleate and 2(2-ethylhexyloxy) 5 ethyl 2 oxo 4 propyl1,3,2 dioxa phosphorinane heat and light stabilizers, to form a slurry.The temperature of the slurry was raised to about 70 C., accompanied bycontinued agitation, so as to effect solvation, thereby forming ahomogeneous solution. The solution was then filtered under pressure andmetered through a spinnerette having 80 holes, each 0.13 millimeter indiameter. The multifilament yarn thus produced from the blend of theconventional fiber-formingacrylonitrile polymer and the copolymerproduct of this example, containing approximately percent by weight ofthe copolymer based upon the total Weight of the polymer blend, wasthereafter coagulated in an aqueous bath containing 15 percentacetonitrile, withdrawn from the bath, washed with a dilute aqueoussolution of hydroxyethylated poly- (vinyl alcohol), stretched 300percent at a temperature of about 60 C., and finally dried and annealedat temperatures up to about 150 C. (yarn I). A control yarn (yarn II)was spun in a similar manner for comparison purposes from the sameconventional, fiber-forming acrylonitrile terpolymer, containing thesame heat and light stabilizers, but omitting the use of the copolymerof this example.

Samples of knit fabrics prepared from each of the above yarns were dyedwith an acid dyestutf, Xylene Milling Blue GL (Color Index 50, 315), bythe well known cuprous-ion technique wherein cupric ions introduced intothe dye bath as cupric sulfate are reduced to the cuprous state with anysuitable reducing agent, such as hydroxyl-ammonium sulfate, zincformaldehyde sulfoxylate, glyoxal, etc., to enhance the dyeability ofacrylonitrile containing yarns. The dye bath was prepared as follows,with all material based on the weight of the fabric:

Percent .Xylene Milling Blue GL 4 Oupric sulfate 2 'I-Iydroxylammoniumsulfate 1 Methyl polyethanol quaternary amine surfactant 1 Samples ofknit fabrics prepared from each of the yarns were dyed in separateboiling dye baths using a dye bath liquor to fabric ratio of 30milliliters per gram. After about 2 hours at the boil, during which timea constant dye bath volume was maintained, the fabrics were removed fromthe dye baths, scoured, rinsed and dried. The knitted fabric preparedfrom the blended polymer composition of this example (yarn I) was dyed adeep blue shade, and dye absorption values determined by Procedure A,above, after completion of the dyeing indicated that 66 percent of thedye available in the dye bath had been absorbed by the fabric. Thecontrol fabric (yarn II), however, was dyed a lighter blue shade, anddye absorption values determined in similar manner indicated that only45 percent of the available dye had been absorbed by the fabric. Thus,the dye absorption of the fibers produced from the polymer blend of thisexample was 46 percent greater than that of the fibers produced from thecontrol, unmodified acrylonitrile terpolymer.

In similar manner, dye aflinity is improved by blending theacrylonitrile terpolymer with a methyl methacrylate/ (2acryloxyethyl)dimethylsulfonium methylsulfate copolymer, an ethylacrylate/ (2-acryl0xyethyl)dimethylsulfonium methylsulfate copolymer, acyanoethyl acrylate/ (2 acryloxyethyl)dimethylsulfonium methylsulfatecopolymer and a vinyl acetate/(Z-acryloxyethyl)dimethylsulfoniummethylsulfate copolymer in accordance with this invention.

Example IV In a manner similar to that described in Example III, 5.6grams of chloroacetic acid were reacted in 150 grams of acetonitrilewith 20 grams of a methylacrylate/Z- methylthioethyl methacrylatecopolymer at a temperature of 50 C. for a period of 20 hours. Thecopolymer employed was comprised of approximately 78 percent by weightof polymerized methyl acrylate and 22 percent by weight of polymerizedZ-methylthioethyl methacrylate, and had a reduced viscosity of 1.64. Theresulting polymer product was coagulated in and washed with isopropylether, and subsequently dried at a temperature of 50 C. in anair-circulating oven. There were thus obtained 23.3 grams of aterpolymer comprised of approximately 72 percent by weight ofpolymerized methyl acrylate, 25 percent by weight of polymerized(Z-methamyloxyethyl)carboxymethylmethylsulfonium chloride and 3 percentby weight of polymerized Z-methylthioethyl methacrylate, i.e.approximately 88 mole percent of methyl acrylate, 10 mole percent of(Z-methacryloxyethyl)carboxymethylmethylsulfonium chloride and 2 molepercent of 2-methylthioethy1 methacrylate in polymerized form, on atheoretical monomer basis. The terpolymer product had a reducedviscosity of 1.71, and was found to contain 4.24 percent by weight ofsulfur and 3.4 percent by weight of chlorine.

The terpolymer product of this example Was subsequently employed toimprove the dye affinity of fibers produced from a conventional,fiber-forming acrylonitrile polymer, and evaluated as such, in themanner described above in Example III, i.e substituting the terpolymerproduct of this example for the coplymer product of Example III underotherwise identical conditions. A sample of knit fabric thus preparedfrom the blended polymer composition of this example was dyed a deepblue shade, and dye absorption values indicated that 79 percent of theavailable dye had been absorbed by the fabric. The control fabric,however, was dyed a lighter blue shade, and dye absorption valuesindicated that only 43 percent of the available dye had been absorbed bythe fabric. Hence, the dye absorption of the fibers produced from thepolymer blend of this example was 84 percent greater than that of thefibers produced from the control, unmodified acrylonitrile polymer.

When a dye bath containing 3 percent Sevron Brilliant Red 4G (a cationicdyestutf) and 1 percent of a tetradecyl sodiumsulfonate surfactant basedupon the weight of fabric was substituted for the Xylene Milling B-lueBL dye bath employed above in this example, a sample of [knit fabricprepared from the blended polymer composition of this example Was dyed amedium red shade, and dye absorption values determined by Procedure B,above, indicated that 41 percent of the available dye had been absorbedby the fabric. On the other hand, the control fabric was dyed a lightred shade, and dye absorption values indicated that only 8 percent ofthe available dye had been absorbed by the fabric. In this case, the dyeabsorption of the fibers produced from the polymer blend of the examplewas 413 percent greater than that of the fibers produced from thecontrol, unmodified acrylonitrile polymer. 7

In similar manner, dye affinity is improved by blending theacrylonitrile polymer with poly[(2-acry1oxyethyl)carboxymethylmethylsulfonium chloride] in accordance with thisinvention.

Example V In a manner similar to that described in Example III, 4.6grams of dimethyl sulfate Were reacted in grams of acetonitrile with18.5 grams of a methyl acrylate/2,3- bis(methylthio)propyl methacrylatecopolymer at a temperature of 50 C. for a period of 22 hours. Thecopolymer employed was comprised of approximately 78 percent by weightof polymerized methyl acrylate and 22 percent by weight of polymerized2,3-bis(methylthio) propyl methacrylate, and had a reduced viscosity of1.66. The amount of dimethyl sulfate employed was sufficient to convertessentially all of the polymerized 2,3-bis(methyl thio)propylmethacrylate to the corresponding polymerized form of3-methacryloxypropyl-1,2-bis(dimethylsulfonium) di(methylsulfate). Theresulting polymer product was coagulated in and washed with isopropylether, and subsequently dried at a temperature of 50 C. in anair-circulating oven. There were thus obtained 24.9 grams of a copolymercomprised of approximately 68 percent by weight of polymerized methylacrylate and 32 percent by weight of polymerized3-methacryloxypropyl-l,2- bis(dimethylsulfonium) di(methylsulfate), i.e.approxi- 1 1 mately 90 mole percent of methyl acrylate and mole percentof 3-methacryloxypropyl-1,2-bis(dimethylsulfonium) di(methylsulfate) inpolymerized form, on a theoretical monomer basis. The copolymer producthad a reduced viscosity of 2.6, and was found to contain 8.59 percent byweight of sulfur.

When blended with a conventional, fiber-forming acrylonitrile polymer asdescribed above in Example IIL'the copolymer product of this examplesubstantially improves the dye aflinity of fibers produced therefrom. Insimilar manner, dye afiinity is improved by blending the acrylonitrilepolymer with poly[3-methacryloxypropyl-1,Z-bis(carboxymethylmeythlsulfoniurn) dichloride] in accordance with thisinvention.

Example VI In a manner similar to that described in Example I, 2.52grams of dimethyl sulfate were reacted in grams of acetone with 2.92grams of poly(2-methylthioethyl acrylate) having a reduced viscosity of1.9, at a temperature of 50 C., for a period of 17 hours. The amount ofdimethyl sulfate employed was sufiicient to convert essentially all ofthe polymerized 2-rnethylthioethyl acrylate to the correspondingpolymerized form of (2-acryloxyethyl)dimethylsulfonium methyl sulfate.The resulting polymer product was insoluble in the acetone and depositedas an opaque film on the walls of the pressure bottle. The acetone wasthen decanted and the polymer product was readily dissolved in 30milliliters of water. About one third of the aqueous solution was usedto cast a film of the polymer on a glass plate, such a film beinguseful, for example, as packaging material. The remainder of the polymerin solution was coagulated in and washed with acetone, and subsequentlydried at a temperature of 50 C. in an air-circulating oven. There werethus obtained 3.9 grams of poly[(2-acryloxyethyl)dimethylsulfoniummethylsulfate] When blended with a conventional fiber-formingacrylonitrile polymer as described above in Example III, the polymerproduct of this example substantially improves the dye affinity offibers produced therefrom. In similar manner, dye aflinity is improvedby blending the acrylonitrile polymer withpoly[(Z-acryloxyethyl)methylethylsulfonium methylsulfate] in accordancewith this invention.

Example VII In a manner similar to that described in Example I, 26 gramsof chloroacetic acid were treated in 150 grams of acetonitrile and gramsof acetone with 20 grams of poly(2-methy1thioethyl acrylate) having areduced viscosity of 1.7, at a temperature of 90 C., for a period of 16hours. The resulting polymer product was coagulated in and washed withisopropyl ether, and subsequently dried at a temperature of 50 C. in anair-circulating oven. There were thus obtained 20.7 grams of copolymercomprised of approximately 75 percent by weight of 2- methylthioethylacrylate and 25 percent by weight of (2-acryloxyethyl)carboxymethylmethylsulfonium chloride, i.e. approximately84 mole percent of 2-methylthioethyl acrylate and 16 mole percent of(Z-acryloxyethyl)carboxymethylrnethylsulfonium chloride in polymerizedform, on a theoretical monomer basis. The copolymer product was found tocontain 3.9 percent by weight of chlorine.

When blended with a conventional fiber-forming acrylonitrile polymer asdescribed above in Example 111, the copolymer product of this examplesubstantially improves the dye affinity of fibers produced therefrom. Insimilar manner, dye affinity is improved by blending the acrylonitrilepolymer with a methyl acrylate/(Z-acryloxyethyl) dimethylsulfoniummethylsulfate copolymer in accordance with this invention.

Example VIII A 300 milliliter Pyrex pressure bottle was charged with17.2 grams of poly(2-methylthioethyl acrylate), have a reduced viscosityof 1.7, 50 grams of acetonitrile and 50 grams of acetone, capped andtumbled in a constant temperature rotary water bath maintained at atemperature of 50 C. until a homogeneous solution was obtained. Thesolution was divided into three equal portions, which were placed inthree similar pressure bottles (A, B and C). To bottle A there wereadded 4.95 grams of dimethyl sulfate; to bottle B there were added 3.75grams of dimethyl sulfate; and to bottle C there were added 2.5 grams ofdimethyl sulfate. Each of the bottles were then capped and heated in awater bath maintained at a temperature of 50 C. for a period of 16hours. The resulting polymer products formed in each of the bottlesseparated from solution, and were redissolved by the addition of 50milliliters of water to each bottle. The polymer products were thencoagulated in and washed with acetone, and subsequently dried at atemperature of 50 C. in an aircirculating oven. There were thus obtainedfrom bottle A, 9.9 grams of poly(2-acryloxyethyldimethylsulfoniummethylsulfate); from bottle B, 8.3 grams of a copolymer comprised ofapproximately 75 mole percent of polymerized(2-acryoxyethyl)dimethylsulfonium methylsulfate and 25 mole percent ofpolymerized Z-methylthioethyl acrylate, on a theoretical monomer basis;and from bottle C, 5.8 grams of a copolymer comprised of approximately50 mole percent of polymerized (2-acryloxyethyl)dimethylsulfoniummethylsulfate and 50 mole percent of polymerized Z-methylthioethylacrylate, on a theoretical monomer Ibasis. Each of these polymerproducts are useful in improving the dye affinity of fibers formed fromconventional fiber-forming acrylonitrile with polymers when blendedtherewith in accordance with this invention.

What is claimed is:

1. The alpha-ethylenically unsaturated sulfine of the formula:

3. (Z-methacryloxyethyl)dimethylsulfonium fate of the formula:

methylsul- 4. (2- acryloxyethyl)methylethylsulfonium methylsulfate ofthe formula:

H CHiCHa CHZ=OHCOCH CHZ? O S OaOHa 5. (2methacryloxyethyl)carboxymethylmethylsulfonium chloride of the formula:

di(methylsulfate) of the formula:

13 6. 3-methacryloxypropyl 1,2 bis(dimethylsulfoniurn) wherein R is amember selected from the group consisting of hydrogen and methyl, R is asaturated aliphatic hydrocarbon radical of from 1 to 4 carbon atoms, Ris alkyl of from 1 to 4 carbon atoms; R is a member selected from thegroup consisting of methyl and carboxymethyl, X is a member selectedfrom the group consisting of methylsulfate, bromine, iodine andchlorine, such that X is chlorine when R is carboxymethyl, and m is aninteger of from 1 to 2.

8. S o l i d poly[ (2 acryloxyethyl)dimethylsulfonium methylsulfate] 9.Solid poly[ (2 acryloxyethyl)carboxymethylmethyb sulfonium chloride].

10. Solid poly[3-methacryloXypropyl-1,2-bis'(dimethylsulfonium)di(methylsulfate) 11. The solid interpolymer consisting essentially of(A) a polymerized alpha-ethylenically unsaturated sulfine of theformula:

R R oanaataalmxwherein R is a member selected from the group consistingof hydrogen and methyl, R is a saturated aliphatic hydrocarbon radicalor from 1 to 4 carbon atoms, R is alkyl of from 1 to 4 carbon atoms, Ris a member selected from the group consisting of methyl andcarboxymethyl, X is a member selected from the group consisting ofmethylsulfate, bromine, iodine and chlorine, such that X is chlorinewhen R is carboxymethyl, and m is an integer of from 1 to 2; and (B) apolymerized alpha-ethylenically unsaturated thioether of the formula:

R 0 I II I 1 OHz=CCOR -S-R wherein R, R R and m are as defined above;said interpolymer containing, in polymerized form and on a theoreticalmonomer basis, at least about mole percent of said alpha-ethylenicallyunsaturated sulfine.

12. The solid interpolymer consisting essentially of (A) a polymerizedalpha-ethylenica'lly unsaturated sulfine of the formula:

wherein R is a member selected from the group consisting of hydrogen andmethyl, R is a saturated aliphatic hydrocarbon radical or from 1 to 4carbon atoms, R is alkyl of from 1 to 4 carbon atoms, R is a memberselected from the group consisting of methyl and carboxymethyl, X is amember selected from the group consisting of methylsulfate, bromine,iodine and chlorine, such that X is chlorine when R is carboxymethyl,and m: is an integer of from 1 to 2; and (B) a polymerizedalpha-ethylenically unsaturated thioether of the formula:

wherein R, R R and m are as defined above; said interpolymer containing,in polymerized form and on a theoretical monomer basis, at least about50 mole percent of said alpha-ethylenically unsaturated sulfine.

13. The solid copolymer of (2-acryloxyethyl)dimethylsulfoniummethylsulfate with 2-methylthioethyl acrylate containing, in polymerizedform and on a theoretical monomer basis, at least about 10 mole percentof said (Z-acryloxyethyl)dimethylsulfonium methylsulfate.

14. The solid copolymer of (2-acryloxyethyl)carboxymethylmethylsulfoniumchloride with 2-methylthioethylacrylate containing, in polymerized formand on a theoretical monomer basis, at least about 10 mole percent ofsaid (Z-acryloxyethyl) carb oxymethylmethylsulfonium chloride.

15. The solid copolymer of 3-methacryloxypropyl-1,2-bis(dimethylsulfonium di(methylsulfate) with 2,3-bis (methylthio)propy1methacrylate containing, in polymerized form and on a theoreticalmonomer basis, at least about 10 mole percent of said3-methacryloxypropyl-l,2- bis(dimethylsulfonium) di(methylsulfate).

16. The solid interpolymer consisting essentially of (A) a polymerizedalpha-ethylenically unsaturated sulfine of the formula:

R 0 R CH2=( 'i-OR -S mX- wherein R is a member selected from the groupconsisting of hydrogen and methyl, R is a saturated aliphatichydrocarbon radical or from 1 to 4 carbon atoms, R is alkyl of from 1 to4 carbon atoms, R is a member selected from the group consisting ofmethyl and oarboxymethyl, X is a member selected from the groupconsisting of methyisulfate, bromine, iodine and chlorine, such that Xis chlorine when R is carboxymethyl, and m is an integer of from 1 to 2;and (B) :a polymerized alpha-ethylenically unsaturated comonomerselected from the group consisting of (a) acrylonitrile, (b) a compoundof the formula:

0 R iooH=oH,

wherein R is alkyl of from 1 to 7 carbon atoms, and (c) a compound ofthe formula:

wherein R is as defined above and R is a member selected from the groupconsisting of alkyl and cyanoalkyl of from 1 to 8 carbon atoms; saidinterpolymer containing, in polymerized form and on a theoreticalmonomer basis, at least about 1 mole percent of said alpha-ethylenically unsaturated su'lfine.

17. The solid interpolymer consisting essentially of (A) a polymerizedalpha-ethylenically unsaturated sulfine of the formula:

wherein R is a member selected from the group consisting of hydrogen andmethyl, R is a saturated aliphatic hydrocarbon radical of from 1 to 4carbon atoms, R is alkyl of from 1 to 4 carbon atoms, R is a memberselected from the group consisting of methyl and carboxymethyl, X is amember selected from the group consisting of methylsulfate, bromine,iodine and chlorine, such that X is chlorine when R is carboxymethyl,and m is an integer of from 1 to 2; and (B) a polymerizedalpha-ethylenioally unsaturated comonomer selected from the groupconsisting of (a) acrylonitrile, (b) a compound of the formula:

wherein R is alkyl of from 1 to 7 carbon atoms, and (c) a compound ofthe formula:

CHz=( J C OR" wherein R is as defined above and R is 'a member selectedfrom the group consisting of alkyl and cyanoalkyl of from 1 to 8 carbonatoms; said interpolymer containing in polymerized form, on atheoretical monomer basis, from about 5 to about 95 mole percent of saidalphaethylenioally unsaturated sulfine.

18. The solid copolymer of (2-methacryloxyethyl)dimethylsulfoniummethylsulfate with methyl acrylate containing, in polymerized form andon a theoretical monomer basis, from about 5 to about 95 mole percent ofsaid (Z-methacryloxyethyl)dimethylsulfonium methylsulfate.

19. The solid copolymer of(2-methacryloxyethy1)carboxymethylmethylsulfonium chlorine with methylacrylate containing, in polymerized form and on a theoretical monomerbasis, from about 5 to about 95 mole percent of said(Z-methacryloxyethyl)carboxymethylmethylsulfonium chloride.

20. The solid copolymer of 3-methac-ryloxypropyl-1,2-bis(dimethylsulfonium) di(methylsulfate) with methyl acrylatecontaining, in polymerized form and on .a theoretical monomer basis,from about 5 to about 95 mole percent of said3-methacryloXypropyl-1,2-bis(dimethylsulfonium) di(methylsulfate).

21. The solid interpolymer consisting essentially of (A) a polymerizedalpha-ethylenically unsaturated sulfine of the formula:

wherein R is a member selected from the group consisting of hydrogen andmethyl, R is a saturated aliphatic hydrocarbon radical of from 1 to 4carbon atoms, R is alkyl of from 1 to 4 carbon atoms, R is a memberselected from the group consisting of methyl and carboxymethyl, X is amember selected from the group consisting of methylsulfate, bromine,iodine and chlorine, such that X is chlorine when R is carboxymethyl,and m is an integer of from 1 to 2; (B) a polymerizedalpha-ethylenically unsaturated thioether of the formula:

wherein R, R R and m are as defined above, and (C) a polymerizedalpha-ethylenically unsaturated comonomer selected from the groupconsisting of (a) acrylonitrile, (b) a compound of the formula:

wherein R is alkyl of from 1 to 7 carbon atoms, and (c) a compound ofthe formula:

No references cited.

JOSEPH L. SCHOFER, Primary Examiner.

D. K. DENENBERG, Assistant Examiner.

1. THE ALPHA-ETHYLENICALLY UNSATURATED SULFINE OF THE FORMULA: